Olefin polymer and process for producing the same

ABSTRACT

An olefin polymer of an alkenyl hydrocarbon having 5 or more carbon atoms, wherein said olefin polymer is an amorphous polymer having a Mn of 300,000 and a Mw/Mn of 2.40 or less, and substantially not having a melting point, and a process for producing said olefin polymer which comprises polymerizing an alkenyl hydrocarbon having 5 or more carbon atoms with an olefin polymerization catalyst obtained by contacting: a specific transition metal compound(A), an organoaluminumoxy compound (B) soluble in an aromatic solvent and water (C).

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a specified amorphous polymerand a process for producing the same. More specifically, the presentinvention relates to an amorphous polymer having a high molecular weightenough to improve problems such as stickiness, elution to an organicsolvent and the like, and to exhibit an elastomeric property andsubstantially not having a melting point and a process for producingsaid amorphous polymer.

[0003] 2. Description of Related Arts

[0004] An amorphous poly(α-olefin)(for example, an atactic polypropyleneand an atactic poly(1-butene)) has been mainly used as a sticking agent,an improving agent for a crystalline polyolefin and the like. However,the molecular weight of an amorphous poly(α-olefin), as known well, isnot high enough, therefore the amorphous poly(α-olefin) has problemssuch as stickiness of a product, elution to an organic solvent and thelike, and it is difficult to say that an elastomeric property issufficiently exhibited.

[0005] With respect to a synthesis of the amorphous polymer, Someprocesses have been known. It has been known from old times that alow-crystalline polymer prepared as a by-product is recovered when anolefin is polymerized with a solid Ziegler-Natta catalyst and anisotactic polymer is produced. However, the polymer obtained then has alow molecular weight and wide molecular weight distribution, and therehave been problems such as stickiness of a product, elution to anorganic solvent and the like.

[0006] Further, there are a report (Chem. Commun., 1996, 783) in which ahigh molecular weight poly(1-hexene)(Mn=1,252,000, Mw/Mn=2.70) can besynthesized by polymerizing 1-hexene under a ultra-high pressure of 250Mpa with a catalyst composed of using a hafnocene dichloride compoundand methyl aluminoxane, and a report (EP0604917 A2 and EP0604908 A2) inwhich a polypropylene having a weight average molecular weight Mw of377,000, a molecular weight distribution Mw/Mn(number average molecularweight) of 2.64 and a viscosity [η] of 2.28 dl/g, and a poly(1-butene)having a viscosity [η] of 1.29 dl/g, can be synthesized by polymerizingpropylene with a catalyst composed of dimethylsilylene bis(9-fluorenyl)zirconium dichloride and methyl alumoxane, but a polymer having anadequate high molecular weight and narrow molecular weight distributionis not obtained.

[0007] On the other hand, a polymer having a Mw of more than 8×10⁶ canbe synthesized (Macromolecular Chemie, Rapid Communication, Vol.10(1989), page 349) by polymerizing propylene using a transition metalcompound having an aryloxy ligand as a catalyst component, but the glasstransition temperature of the polymer was somewhat high and anelastomeric property was not sufficient. Further, in the polymerizationof an olefin having 5 or more carbon atoms with such catalyst, theresulted polymer was also not always satisfactory in the points ofstickiness and elution property to an organic solvent.

[0008] As described above, a poly(α-olefin of 5 or more carbon atoms)which has an adequate high molecular weight and narrow molecular weightdistribution and no melting point substantially, and is amorphous, isnot obtained.

SUMMARY OF THE INVENTION

[0009] An object of the present invention is to provide an amorphouspolymer having a high molecular weight enough to improve problems suchas stickiness, elution to an organic solvent and the like, and toexhibit an elastomeric property, and substantially not having a meltingpoint.

[0010] Another object of the present invention to provide a process forproducing said amorphous polymer.

[0011] Other objects and advantages of the present invention will beapparent from description below.

[0012] The present inventors have intensively studied to attain theabove-mentioned objects, and as a result, completed the presentinvention.

[0013] According to the present invention, there are provided an olefinpolymer of an alkenyl hydrocarbon having 5 or more carbon atoms, whereinsaid olefin polymer is an amorphous polymer having a polystyrene-reducednumber average molecular weight of 300,000 and a molecular weightdistribution of 2.40 or less in terms of a ratio of polystyrene-reducedweight average molecular weight (hereinafter, sometimes referred to as“Mw”) to polystyrene-reduced number average molecularweight(hereinafter, sometimes referred to as “Mn”) [Mw/Mn], andsubstantially not having a melting point, and a process for producingsaid olefin polymer which comprises polymerizing an alkenyl hydrocarbonhaving 5 or more carbon atoms with an olefin polymerization catalystobtained by contacting:

[0014] a transition metal compound (A) represented by the generalformula (1) described below;

[0015] an organoaluminumoxy compound (B) soluble in an aromatic solvent;and

[0016] water (C), wherein the molar ratio of aluminum atom contained inthe organoaluminumoxy compound (B) to a transition metal atom containedin the transition metal compound (A) is 1 to 20000, and the amount ofwater used is 0.1 to 3.0 mol per 1 mol of aluminum atom contained in theorganoaluminumoxy compound (B).

[0017] (wherein M represents a transition metal atom of the Fourth Groupof the Periodic Table, X and Y independently represent a hydrogen atom,a halogen atom, an alkyl group, an aryl group, an aralkyl group, analkoxy group, an aryloxy group, an aralkyloxy group, a sulfonyloxygroup, a di-substituted amino group or a substituted silyl group. R¹,R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independently represent a hydrogen atom,an alkyl group, an aryl group, an aralkyl group, an alkoxy group, anaryloxy group, an aralkyloxy group, a di-substituted amino group or asubstituted silyl group. Further, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ maybe optionally bonded to form a ring. T represents a divalent covalentcrosslinking group having 1 to 20 carbon atoms, or a divalent grouprepresented by —O—, —S—, —S—S—, —S(═O)—, —S(═O)₂—, —C(═O)—, —N(R⁹)—,—P(R⁹)—, or —P(═O)(R⁹)— (wherein R⁹ represents a hydrogen atom or ahydrocarbon group having 1 to 6 carbon atoms in each case), n is aninteger of from 0 to 3.).

BRIEF DESCRIPTION OF THE DRAWING

[0018]FIG. 1 is a flow chart to aid the understanding of the presentinvention. The flow chart is a representative example of the mode ofoperation of the present invention, and the present invention is notlimited thereto.

DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention is explained in detail below.

[0020] An olefin polymer of the present invention is a polymer of analkenyl hydrocarbon having 5 or more carbon atoms and an amorphouspolymer having a Mn of 300,000 or more and a Mw/Mn of 2.40 or less, andsubstantially not having melting point.

[0021] Specific examples of the alkenyl hydrocarbon having 5 or morecarbon atoms, include an α-olefin having 5 or more carbon atoms such as1-pentene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-penetene,4-methyl-1-penete, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and thelike, and vinylcyclohexane, and the like, and an alkenyl hydrocarbonhaving 5 to 20 carbon atoms is preferred. As the alkenyl hydrocarbonhaving 5 or more carbon atoms, a linear α-olefin is more preferable, and1-hexene or 1-octene is most preferable.

[0022] The olefin polymer of the present invention may be a copolymer.As a comonomer constituting the copolymer, a monomer copolymerizablewith the alkenyl hydrocarbon having 5 or more carbon atoms, excluding1-butene, can be used, and propylene or another alkenyl hydrocarbonhaving 5 or more carbon atoms is preferable.

[0023] The content of the alkenyl hydrocarbon having 5 or more carbonatoms in the polymer of the present invention is preferably 20 mol % ormore, more preferably 50 mol % or more, and particularly preferable 70mol % or more. Further, the most preferable olefin polymer of thepresent invention is a homopolymer of 1-hexene (poly(1-hexene)) or ahomopolymer of 1-octene (poly(1-octene)).

[0024] The Mn of the olefin polymer of the present invention is 300,000or more, preferably 500,000 or more, and more preferably 800,000 ormore. When the Mn of the olefin polymer is less than 300,000, it is notpreferable because problems such as stickiness and elution to an organicsolvent sometimes happen to occur.

[0025] Herein, the Mn described above and Mw described below mean apolystyrene-reduced number average molecular weight and apolystyrene-reduced weight average molecular weight, respectively,measured by gel permeation chromatography method.

[0026] The olefin polymer of the present invention has a Mw/Mn of 2.40or less, preferably 2.3 or less, and more preferably 2.2 or less. Whenthe Mw/Mn exceeds 2.40, it is not preferable because problems such asstickiness and elution to an organic solvent sometimes happen to occur.

[0027] The olefin polymer of the present invention is an amorphouspolymer substantially not having a melting point. The melting point isusually measured with a differential scanning calorimeter (DSC) or thelike. In the present invention, the term “substantially not having amelting point” means that a crystal melting peak or crystallization peakis not substantially observed in the DSC measurement.

[0028] Such olefin polymer can be produced using, for example, saidolefin polymerization catalyst obtained by contacting a transition metalcompound (A) represented by the general formula (1) described above, anorganoaluminumoxy compound (B) soluble in an aromatic solvent, and water(C).

[0029] In the fore-mentioned general formula (1), M represents atransition metal atom of the Fourth Group of the Periodic Table (IUPACInorganic Chemistry Nomenclature, a revised edition, 1989) of elements,and a titanium atom, a zirconium atom or a hafnium atom is preferableand a titanium atom is more preferable.

[0030] In the general formula (1), respective X and Y independentlyrepresent a hydrogen atom, a halogen atom, an alkyl group, an arylgroup, an aralkyl group, an alkoxy group, an aryloxy group, anaralkyloxy group, a sulfonyloxy group, a di-substituted amino group or asubstituted silyl group.

[0031] Specific examples of such halogen atoms include a chlorine atom,a bromine atom, an iodine atom and the like, and a chlorine atom ispreferable.

[0032] As the alkyl group in X or Y of the above-mentioned generalformula (1), an alkyl group hydrocarbon having 1 to 24 carbon atoms ispreferable. Specific examples thereof include methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, sec-butyl group,tert-butyl group, n-pentyl group, neo-pentyl group, iso-pentyl group,1-methylbutyl group, n-hexyl group, n-octyl group, n-decyl group,n-dodecyl group, n-pentadecyl group, n-eicosyl group, and the like.Methyl group, ethyl group, isopropyl group, tert-butyl group, n-pentylgroup, neo-pentyl group or iso-pentyl group is preferable.

[0033] Any one of these alkyl groups may be substituted with halogenatoms such as a fluorine atom, chlorine atom, bromine atom and iodineatom, alkoxy groups such as methoxy group, ethoxy group and the like,and aryloxy groups such as phenoxy group and the like.

[0034] Examples of the alkyl group having 1 to 24 carbon atoms which issubstituted with a halogen atom include a fluoromethyl group, adifluoromethyl group, trifluoromethyl group, a chloromethyl group, adichloromethyl group, trichloromethyl group, a bromomethyl group, adibromomethyl group, tribromomethyl group, an iodomethyl group, adiiodomethyl group, triiodomethyl group, a fluoroethyl group, adifluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group,pentafluoroethyl group, a chloroethyl group, a dichloroethyl group, atrichloroethyl group, a tetrachloroethyl group, pentachloroethyl group,a bromoethyl group, a dibromoethyl group, a tribromoethyl group, atetrabromoethyl group, a pentabromoethyl group, a perfluoropropyl group,a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group,a perfluorooctyl group, a perfluorododecyl group, a perfluoropentadecylgroup, a perfluoroeicosyl group, a perchloropropyl group, aperchlorobutyl group, a perchloropentyl group, a perchlorohexyl group, aperchlorooctyl group, a perchlorododecyl group, a perchloropentadecylgroup, a perchloroeicosyl group, a perbromopropyl group, a perbromobutylgroup, a perbromopentyl group, a perbromohexyl group, a perbromooctylgroup, a perbromododecyl group, a perbromopentadecyl group, aperbromoeicosyl group, and the like. When various isomers exist, suchisomers are included.

[0035] Further, as the aryl group in X or Y in the general formula (1)described above, an aryl group having 6 to 24 carbon atoms ispreferable, and specific examples thereof include phenyl group, 2-tolylgroup, 3-tolyl group, 4-tolyl group, a 2,3-xylyl group, a 2,4-xylylgroup, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylylgroup, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group,2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group,3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group,pentamethylphenyl group, an ethylphenyl group, a n-propylphenyl group, aiso-propylphenyl group, a n-butylphenyl group, a sec-butylphenyl group,a tert-butylphenyl group, a n-pentylphenyl group, a neo-pentylphenylgroup, a n-hexylphenyl group, naphtyl group, an antharcenyl group, andthe like, and phenyl group is preferable. Any one of these aryl groupsmay be substituted with a halogen atom such as a fluorine atom, chlorineatom, bromine atom or an iodine atom, an alkoxy group such as methoxygroup, ethoxy group or the like, and an aryloxy group such as phenoxygroup or the like.

[0036] As the aralkyl group in X or Y in the general formula (1)described above, an aralkyl group having 7 to 24 carbon atoms ispreferable, and specific examples thereof include benzyl group,(2-methylphenyl)methyl group, (3-methylphenyl)methyl group,(4-methylphenyl)methyl group, (2,3-dimethylphenyl)methyl group,(2,4-dimethylphenyl)methyl group, (2,5-dimethylphenyl)methyl group,(2,6-dimethylphenyl)methyl group, (3,4-dimethylphenyl)methyl group,(4,6-dimethylphenyl)methyl group, (2,4,6-trimethylphenyl)methyl group,(pentamethylphenyl)methyl group, a (ethylphenyl)methyl group, a(n-propylphenyl)methyl group, a (n-butylphenyl)methyl group, a(sec-butylphenyl)methyl group, a (tert-butylphenyl)methyl group, a(n-pentylphenyl) methyl group, a (neo-pentylphenyl)methyl group,naphtylmethyl group, antharcenylmethyl group and the like, and benzylgroup is preferable. Any one of these aralkyl groups may be substitutedwith a halogen atom such as a fluorine atom, a chlorine atom, a bromineatom or an iodine, an alkoxy group such as methoxy group, ethoxy groupor the like, and an aryloxy group such as phenoxy group or the like.

[0037] As the alkoxy group in X or Y in the general formula (1)described above, an alkoxy group having 1 to 24 carbon atoms ispreferable, and specific examples thereof include methoxy group, ethoxygroup, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxygroup, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxygroup, n-octoxy group, n-dodecoxy group, n-pentadecoxy group, n-icosoxygroup, and the like, and methoxy group, ethoxy group or tert-butoxygroup is preferable.

[0038] Any one of these alkoxy groups may be substituted with a halogenatom such as a fluorine atom, a chlorine atom, a bromine atom, or aniodine atom.

[0039] Further, as the aryloxy group in X or Y in the general formula(1) described above, an aryloxy group having 6 to 24 carbon atoms ispreferable and specific examples thereof include phenoxy group,2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group,2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group,2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group,3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group,2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group,2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group,2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group,2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group,2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, anethylphenoxy group, a n-propylphenoxy group, an isopropylphenoxy group,a n-butylphenoxy group, a sec-butylphenoxy group, a tert-butylphenoxygroup, a n-hexylphenoxy group, a n-octylphenoxy group, a n-decylphenoxygroup, a n-tetradecylphenoxy group, a naphtoxy group, an antharcenoxygroup and the like. Phenoxy group is preferable. Any one of thesearyloxy groups may be substituted with a halogen atom such as a fluorineatom, chlorine atom, bromine atom or iodine atom.

[0040] As the aralkyloxy group in X or Y in the above-mentioned formula(1) described above, an aralkyloxy group having 7 to 24 carbon atoms ispreferable , and specific examples thereof include a benzyloxy group,(2-methylphenyl)methoxy group, (3-methylphenyl)methoxy group,(4-methylphenyl)methoxy group, (2,3-dimethylphenyl)methoxy group,(2,4-dimethylphenyl)methoxy group, (2,5-dimethyphenyl )methoxy group,(2,6-dimethylphenyl)methoxy group, (3,4-dimethylphenyl)methoxy group,(3,5-dimethylphenyl)methoxy group, (2,3,4-trimethylphenyl)methoxy group,(2,3,5-trimethylphenyl)methoxy group, (2,3,6-trimethylphenyl)methoxygroup, (2,4,5-trimethylphenyl)methoxy group,(2,4,6-trimethylphenyl)methoxy group, (3,4,5-trimethylphenyl)methoxygroup, (2,3,4,5-tetramethylphenyl)methoxy group,(2,3,5,6-tetramethylphenyl)methoxy group, (pentamethylphenyl)methoxygroup, an (ethylphenyl)methoxy group, a (n-propylphenyl)methoxy group,an (isopropylphenyl)methoxy group, a (n-butylphenyl)methoxy group, a(sec-butylphenyl)methoxy group, a (tert-butylphenyl)methoxy group, a(n-hexylphenyl)methoxy group, a (n-octylphenyl) methoxy group, a(n-decylphenyl)methoxy group, a n-tetradecylphenyl)methoxy group, anaphtylmethoxy group, an antharcenylmethoxy group and the like, and abenzyloxy group is preferable. Any one of these aralkyloxyl groups maybe substituted with halogen atoms such as a fluorine atom, a chlorineatom, a bromine atom or an iodine atom.

[0041] The sulfonyloxy group in X or Y in the general formula (1)described above represents a group indicated by the general formulaR¹⁰SO₃— and represents a sulfonyloxy group having 1 to 24 carbon atomswhich may be optionally substituted. Specific examples thereof includethose such as methanesulfonyloxy group, ethanesulfonyloxy group,dodecylsulfonyloxy group or the like whose R¹⁰ is an alkyl group, thosesuch as a trifluoromethanesulfonyloxy group or the like whose a part issubstituted with a halogen atom, those such as p-toluenesulfonyloxygroup or the like whose R¹⁰ is an aryl group, or the like.

[0042] As the di-substituted amino group in X or Y in the generalformula (1) described above, a di-substituted amino group having 2-24carbon atoms which is substituted with two hydrocarbon groups ispreferable. Specific examples the hydrocarbon groups include alkylgroups having 1 to 10 carbon atoms such as methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, sec-butyl group,tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group,cyclohexyl group and the like, aryl groups such as phenyl group and thelike, etc. Examples of such di-substituted amino group having 2 to 24carbon atoms include dimethylamino group, diethylamino group,di-n-propylamino group, di-isopropylamino group, di-n-butylamino group,di-sec-butylamino group, di-tert-butylamino group, di-n-octylaminogroup, di-n-decylamino group, di-phenylamino group,bis-trimethylsilylamino group, bis-tert-butyldimethylsilylamino groupand the like, and dimethylamino group or diethylamino group ispreferable.

[0043] As the substituted silyl group in X or Y in the general formula(1) described above, a substituted silyl group having 1 to 24 carbonatoms, in other words, a silyl group substituted with a hydrocarbongroup is preferable. Examples of the hydrocarbon group include, forexample, alkyl groups having 1 to 10 carbon atoms (e.g. methyl group,ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butylgroup, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group,cyclohexyl group), aryl groups (e.g. phenyl group). Examples of suchsilyl group having 1 to 24 carbon atoms include a mono-substituted silylgroup having 1 to 20 carbon atoms such as methylsilyl group, ethylsilylgroup, phenylsilyl group or the like, a disubstituted silyl group having2 to 20 carbon atoms such as dimethylsilyl group, diethylsilyl group,diphenylsilyl group or the like, a trisubstituted silyl group having 3to 20 carbon atoms such as trimethylsilyl group, triethylsilyl group,tri-n-propylsilyl group, tri-isopropylsilyl group, tri-n-butylsilylgroup, tri-sec-butylsilyl group, tri-tert-butylsilyl group,tri-isobutylsilyl group, tert-butyldimethylsilyl group,tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilylgroup, triphenylsilyl group and the like, and trimethylsilyl group,tert-butyldimethylsilyl group or triphenylsilyl group is preferable.

[0044] Any hydrocarbon group of these substituted silyl groups may besubstituted with a halogen atom such as a fluorine atom, chlorine atom,bromine atom or iodine atom.

[0045] These X and Y may optionally be bonded to form a ring. Each of ahalogen atom, an alkyl group or an aralkyl group is independentlypreferable as X and Y in the fore-mentioned general formula (1), andchlorine atom, methyl group or benzyl group is more preferable.

[0046] Respective R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ in thefore-mentioned general formula (1) independently represent a hydrogenatom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group,an aryloxy group, an aralkyloxy group, a di-substituted amino group or asubstituted silyl group. Further, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ mayoptionally be bonded to form a ring. Each of an alkyl group, an arylgroup, an aralkyl group, an alkoxy group, an aryloxy group, anaralkyloxy group, a di-substituted amino group or a substituted silylgroup in R¹, R², R³, R⁴, R⁵, R⁶, R⁷ or R⁸ is similar as in X or Y.

[0047] An aryl group or a substituted silyl group is preferable as R¹,R², R³, R⁴, R⁵, R⁶, R⁷ or R⁸ in the present invention.

[0048] In the fore-mentioned general formula (1), T represents adivalent covalent cross-linking group having 1 to 20 carbon atoms, or adivalent group represented by —O—, —S—, —S—S—, —S(═O)—, —S(═O)₂—,—C(═O)—, —N(R⁹)—, —P(R⁹)—, or —P(═O)(R⁹)— (wherein R⁹ represents ahydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms in eachcase) and n is an integer selected from 0 to 3.)

[0049] As the divalent common cross-linking group having 1 to 20 carbonatoms, methylene group, ethylene group, trimethylene group, propylenegroup, diphenylethylene group, ethylidene group, propylidene group,isopropylidene group, n-butylidene group, isobutylidene group and thelike are exemplified. Among them, methylene group, ethylene group,ethylidene group, isopropylidene group, or isobutylidene group ispreferably used.

[0050] Further, in the divalent group represented by —N(R⁹)—, —P(R⁹)—,or —P(═O)(R⁹)— as T, R⁹ represents a hydrogen atom or a hydrocarbongroup having 1 to 24 carbon atoms in each case. As the hydrocarbongroup, an alkyl group having 1 to 24 carbon atoms, an aryl group having6 to 24 carbon atoms or an aralkyl group having 7 to 24 carbon atoms ispreferable. An alkyl group having 1 to 24 carbon atoms is morepreferable.

[0051] A divalent group represented by —O— or —S— is preferable as T,and —S— is more preferable.

[0052] n is an integer of 0 to 3, and represents the number of the unitT . Among these, 0 or 1 gives a preferable result in particular, and nis more preferably 1.

[0053] The transition metal compound in the fore-mentioned generalformula (1) can be easily produced and isolated. For example, theproduction process (I) and (II) described below are illustrated.

[0054] (I) A process for producing the transition compound by reacting acompound represented by the general formula (2) described below with atransition metal compound represented by the general formula (3)described below.

[0055] (II) A process for producing the transition compound by reactinga compound of the general formula (2) described below with anorganoalkaline metal compound, an alkaline metal hydride compound or anorganomagnesium compound (hereinafter, sometimes referred to as “themetal compound”) to obtain a halide compound and then reacting it withthe transition metal compound represented by the general formula (3)described below.

[0056] The halide compound may not be separated in the process (II).Further, it is also possible in the process (II) to mix together thecompound represented by the general formula (2), the metal compound andthe transition metal compound represented by the general formula (3) andreact them.

[0057] (Wherein respective R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸independently represent a hydrogen atom, an alkyl group, an aryl group,an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxygroup, a di-substituted amino group or a substituted silyl group, R¹,R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ may arbitrarily bond to form a ring, Trepresents a divalent covalent cross-linking group having 1 to 20 carbonatoms, or a divalent group represented by —O—, —S—, —S—S—, —S(═O)—,—S(═O)₂—, —C(═O)—, —N(R⁹)—, —P(R⁹)—, or —P(═O)(R⁹)— (wherein R⁹represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbonatoms in each case), and n is an integer of 0 to 3.)

MZ¹Z²Z³Z⁴  (3)

[0058] (wherein M represents a transition metal atom of the Fourth Groupof the Periodic Table, and respective Z¹, Z², Z³ and Z⁴ independentlyrepresent a halogen atom, an alkoxy group, an aryloxy group, anaralkyloxy group, a di-substituted amino group, an alkyl group, an arylgroup or an aralkyl group.)

[0059] Respective R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and T in the generalformula (2) are the same as in the general formula (1).

[0060] As specific examples of the compound represented by the generalformula (2), 2-(2-hydroxypropyl)phenol, cathecol, resorcinol,4-isopropylcathecol, 3-methoxycathecol, 1,8-dinydroxynaphthalene,1,2-dinydroxynaphthalene, 2,2′-biphenyldiol, 1,1′-bi-2-naphthol,2,2′-dihydroxy-6,6′-dimethylbiphenyl,4,4′,6,6′-tetra-tert-butyl-2,2′-methylenediphenol,4,4′,6,6′-tetramethyl-2,2′-isobutylidenediphenol,2,2′-thiobis(4-methyl-6-isopropylphenol),2,2′-thiobis(4,6-dimethylphenol),2,2′-thiobis(4-methyl-6-tert-butyl)phenol and the like can beexemplified. Among these, 2,4-dihydroxypentane, cathecol,2,2′-biphenyldiol, 1,1′-bi-2-naphthol,4,4′,6,6′-tetra-tert-butyl-2,2′-methylenediphenol,4,4′-dimethyl-6,6′-di-tert-butyl-2,2′-methylenediphenol,4,4′,6,6′-tetramethyl-2,2′-isobutylidenediphenol,2,2′-thiobis(4-methyl-6-isopropyl)phenol),2,2′-thiobis(4,6-dimethylphenol) and2,2′-thiobis(4-methyl-6-tert-butyl)phenol give a preferable result.

[0061] In the transition metal compound represented by theabove-mentioned general formula (3), Z¹, Z², Z³ and Z⁴ independentlyrepresent a halogen atom, an alkoxy group, an aryloxy group, anaralkyloxy group, a sulfonyloxy group, a di-substituted amino group, analkyl group, an aryl group or an aralkyl group. Further, these may beoptionally bonded in part to form a ring.

[0062] Z¹, Z², Z³ and Z⁴ are the same as in X or Y in theabove-mentioned general formula (1). More specific examples of thetransition metal compound represented by the general formula (3) includetitanium halides such as titanium tetrachloride, titanium tetrabromide,titanium tetraiodide and the like, titanium amides such astetrakis(dimethylamino) titanium, dichlorobis(dimethylamino) titanium,trichloro(dimethylamino) titanium, tetrakis(diethylamino) titanium andthe like, alkoxytitaniums such as tetraisopropoxytitanium, tetran-butoxytitanium, diisopropoxytitanium dichloride, isopropoxytitaniumtrichloride and the like, and compounds in which titanium in theabove-mentioned compounds is replaced with zirconium or hafnium, etc.

[0063] In the production process (I) or (II), the amount used of thetransition metal compound represented by the general formula (3) isusually 0.5 to 3-fold mol, and preferably 0.7 to 1.5-fold mol based onthe compound represented by the general formula (2).

[0064] Specific examples of the organoalkaline metal compound used inthe production process (II) include organolithium compounds such asmethyllithium, ethyllithium, n-butyllithium, sec-butyllithium,tert-butyllithium, lithium trimethylenesilyl acetylide, lithiumacetylide, trimethylsilyl methyllithium, vinyllithium, phenyllithium,allyllithium and the like, organoalkaline metal compounds in whichlithium in these compounds is replaced with sodium, potassium, rubidiumor cesium. Preferably, an alkaline metal compound having an alkyl groupwith 1 to 10 carbon atoms is preferred, a compound having an alkyl groupwith 1 to 10 carbon atoms of lithium, sodium or potassium is morepreferred, and an alkyllithium compound having an alkyl group with 1 to10 carbon is most preferred.

[0065] The alkaline metal hydride is a hydride of lithium, sodium,potassium, rubidium or cesium, and sodium hydride or potassium hydrideis preferred.

[0066] Examples of the organomagnesium compound include dialkylmagnesiumcompounds and alkylmagnesium halides, and specifically,dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium,diisopropylmagnesium, n-butylethylmagnesium, methylmagnesium iodide,methylmagnesium chloride, isopropylmagnesium halide and the like.Alkylmagnesium halides having an alkyl group of 1 to 10 carbon atoms arepreferred.

[0067] As the above-mentioned metal compounds, organoalkaline metalcompounds or alkaline metal hydrides are preferable and the alkyllithiumis more preferable. The amount used of the metal compound in theproduction process (II) is usually 1 to 5-fold mol based on the compoundrepresented by the general formula (2).

[0068] The reaction is generally carried out in the presence of asolvent. Examples of the solvent used include an aprotic solvent of anaromatic hydrocarbon such as benzene, toluene, xylene, mesitylene or thelike, an aliphatic hydrocarbon such as pentane, hexane, heptane, octaneor the like, an ether type solvent such as diethyl ether,tetrahydrofuran, 1,4-dioxane or the like, an amide type solvent such ashexamethylphosphoric amide, dimethyl amide, a polar solvent such asacetonitrile, propionitrile, acetone, diethyl ketone, methylisobutylketone, cyclohexanone or the like, a halogenated solvent such asdichloromethane, dichloroethane, chlorobenzene, dichlorobenzene, or thelike, etc. Such solvent is used alone or two or more in combination, andthe amount used thereof is usually 1 to 200 ml/g based on the volume toweight of the compound represented by the general formula (2) andPreferably 3 to 50 ml/g.

[0069] The reaction (I) can be carried out in the presence of atertiaryamine compound or the like, and triethylamine anddiisopropylethylamine, N,N,N′,N′-tetramethylethylenediamine and the likeare preferably used as the tertiaryamine compound as an additive aid.The amount used is 1 to 10-fold mol based a compound represented by thegeneral formula (2), preferably 1.5 to 5-fold mol and more preferably1.8 to 4-fold mol.

[0070] The reaction of the production process (I) is carried out in arange of −100° C. to 200° C., and preferably −80° C. to 150° C. A rangeof −50° C. to 120° C. is more preferable. The reaction temperature inthe production process (II) is usually from −100° C. to the boilingpoint of the solvent used as a medium, but when the organoalkaline metalis used, a range of −80° C. to 40° C. is preferable and when theorganomagnesium compound is used, a range of 10° C. to 100° C. ispreferable, respectively.

[0071] When there is a solid component which is produced as a by-productby the reaction from the reaction mixture containing the transitionmetal compound represented by the general formula (I) according to theabove-mentioned reaction, it is separated by filtration or the like inthe presence of a predetermined solvent, and further, after heating andconcentrating the solvent or by standing alone in another solvent aloneor a mixed solvent at a cooled dark place, crystals of the complex canbe separated. Further, it is possible to efficiently precipitate thedesired complex in high purity to take out, while industrially stirringwithout standing alone, for example, cooling gradually.

[0072] The compound represented by the general formula (2) in thepresent invention is produced by various processes. For example, when Tis a sulfur atom, the compound can be easily synthesized by reactingvarious kind of phenol compounds with sulfur dichloride in a solventwhile stirring.

[0073] The solvent used includes an aprotic solvent of an aliphatichydrocarbon such as pentane, hexane, heptane, octane or the like, anetheral solvent such as diethyl ether, tetrahydrofuran, 1,4-dioxane orthe like, a halogenated hydrocarbon solvent such as dichloromethane,dichloroethane, chlorobenzene, dichlorobenzene or the like, etc.

[0074] The component (B) in the above-mentioned olefin polymerizationcatalyst is an organoaluminumoxy compound soluble in an aromatichydrocarbon solvent. The examples thereof include methylaluminoxane,ethylaluminoxane, propylaluminoxane, butylaluminoxane,isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane,methylisobutylaluminoxane, the organoaluminumoxy compound represented bythe general formula (4) or (5) described below, and the like. Amongthem, methylisobutylaluminoxane, and the organoaluminumoxy compoundsrepresented by the general formula (4) and (5) described below arepreferred.

[0075] (wherein R represents methyl group or isobutyl group, thepresence ratio of a methyl group and an isobutyl group is methyl group:isobutyl group=5 to 95:95 to 5. m represents a number in a range of 1 to50.)

[0076] The organoaluminumoxy compound soluble in an aromatic hydrocarbonsolvent which is used in the present invention can form a componentinsoluble in the aromatic hydrocarbon solvent by reacting with water.

[0077] The amount of the organoaluminumoxy compound used can be usuallyselected in a wide range of 1 to 20,000 mol in terms of an aluminum atomcontained in the organoaluminumoxy compound per one mol of a transitionmetal atom contained in the transition metal compound (A). Thepreferable range is from 100 to 10,000 mol per one mol of the transitionmetal atom.

[0078] Water is used as the component (C) in the above-mentioned olefinpolymerization catalyst. The amount of the water (C) used can be usuallyselected in a wide range of 0.1 to 3.0 mol per one mol of an aluminumatom contained in the organoaluminumoxy compound (B). The preferablerange is from 0.1 to 1.0 per one mol of the aluminum atom.

[0079] As a method of feeding the respective catalyst components in apolymerization reactor, a transition metal compound (A), an aromaticorganoaluminumoxy compound (B) and water (C) may be separately fed ormay be fed after contacting them in advance.

[0080] Specific examples of a method of previously contacting include amethod of contacting an organoaluminumoxy compound (B) with water (C)and then removing the solvent followed by contacting with the component(A), a method of contacting the component (B) with the component (C) andthen contacting with the component (A), a method of contacting thecomponent (A), the component (B) and the component (C) at the same time,and the like. Examples of a contacting method of the component (C)include a method of directly contacting water, a method of previouslymixing water with a solvent and contacting the mixture with othercomponents, a method of contacting a metal salt containing a crystalwater or an inorganic or organic material containing absorbed water withother components, a method of contacting a gas such as nitrogencontaining moisture, or the like with other components, etc. when thecomponent (B) is contacted with the component (C), a component insolublein an aromatic hydrocarbon solvent sometimes form.

[0081] Polymerization is usually carried out over a wide range of −30 to300° C., preferably 0 to 280° C. and more preferably 20 to 250° C.

[0082] The polymerization pressure is not particularly restricted, andis preferably from about normal pressure to about 150 atom fromindustrial and economic viewpoints. The polymerization time is suitablydetermined according to a kind of the desired polymer and a reactionapparatus in general, and adopts a range of 30 seconds to 40 hours.

[0083] As a polymerization process, either of batch type and continuoustype are applicable. Further, a slurry or solution polymerization withan inert hydrocarbon solvent such as propane, pentane, hexane, heptane,octane or the like, a bulk polymerization using a monomer as a solventor a gas phase polymerization is applicable.

[0084] A chain transfer agent such as hydrogen or the like can be addedin order to control the molecular weight of the olefin polymer.

EXAMPLE

[0085] The present invention is specifically illustrated according toExamples below, but the scope of the present invention is not restrictedby Examples.

[0086] The value of respective items in Examples was measured by methodsdescribed below.

[0087] (1) Polystyrene-Reduced Weight Average Molecular Weight (Mw),Polystyrene-Reduced Number Average Molecular Weight (Mn) and MolecularWeight Distribution (Mw/Mn)

[0088] They were measured with a gel permeation chromatograph (GPC)under conditions described below. A calibration curve was prepared usinga standard polystyrene.

[0089] Measuring instrument: 150 CV type manufactured by MilliporeWaters Company Ltd.

[0090] Column: Shodex M/S 80

[0091] Measurement temperature: 145° C.,

[0092] Solvent: Ortho-dichlorobenzene

[0093] Sample concentration: 5 mg/8 ml

[0094] (2) Measurement with a Differential Scanning Calorimeter (DSC)

[0095] It was measured under the conditions below using DSC-VIImanufactured by Perkin-Elmer Company, Ltd.

[0096] Raising temperature: 20° C. to 200° C. (20° C/min.), retentionfor 10 min.

[0097] Cooling: 200° C. to −100° C. (20° C/min.), retention for 10 min.

[0098] Measurement: −100° C. to 300° C. (raising temperature at 20°C./min.)

Reference Example 1

[0099] Synthesis ofDichloro{2,2′-thiobis[4-methyl-6-(tert-butyl)phenolato]} Titanium

[0100] The title compound was synthesized according to a literature(Arjan van der Linden et. al., Journal of the American Chemical Society,117, 3008(1995))

Example 1

[0101] An egg-plant type flask with an inner volume of 300 ml wasreplaced with argon, 20 mmol of (poly)methylisobutyl aluminoxane(hereinafter, sometimes abbreviated to as “MMAO”) manufactured byTosoh-Akzo Co., Ltd. of toluene solution and 11 mmol of water were addedtherein and the mixture was mixed by stirring for 10 minutes.

[0102] On the other hand, in an egg-plant type flask with an innervolume of 25 ml replaced with argon, 5 ml of purified toluene and 1.2 mgof dichloro{2,2′-thiobis[4-methyl-6-(tert-butyl)phenolato} titanium weremixed by stirring, and then charged into the above-mentioned egg-planttype flask. The molar ratio of [Al]/[Ti] of the catalyst solutionprepared then was 8,000. After the catalyst solution was mixed bystirring at room temperature for 10 minutes, 63 ml of 1-hexene wascharged and the polymerization was carried out at 40° C. for 3 minutes.After completion of the polymerization, the contents in the flask werecharged into about 400 ml of an acidic methanol, and the precipitatedpolymer was filtered to be dried at 80° C. for about 2 hours. As aresult, 0.63 g of poly(1-hexene) copolymer was obtained. Mw of thepolymer obtained was 566×10⁴, Mn was 297×10⁴, Mw/Mn was 1.9, no crystalfusion peak by DSC was detected, and the polymer was amorphous. Theglass transition temperature was observed at −46° C.

Example 2

[0103] An egg-plant type flask with an inner volume of 100 ml wasreplaced with argon, 20 mmol of MMAO and 11 mmol of water were addedtherein and the mixture was mixed by stirring for 10 minutes.

[0104] On the other hand, in an egg-plant type flask with an innervolume of 25 ml replaced with argon, 5 ml of purified toluene and 1.2 mgof dichloro{2,2′-thiobis[4-methyl-6-(tert-butyl)phenolato} titanium weremixed by stirring, and then charged into the above-mentioned egg-planttype flask of 100 ml. The molar ratio of [Al]/[Ti] of the catalystsolution prepared then was 8,000. After the catalyst solution was mixedby stirring at room temperature for 10 minutes, 31.2 ml of 1-octene wascharged and the polymerization was carried out at 40° C. for 10 minutes.After completion of the polymerization, the contents of the flask werecharged into about 400 ml of an acidic methanol, and the precipitatedpolymer was filtered to be dried at 80° C. for about 2 hours. As aresult, 0.12 g of poly(1-octene) copolymer was obtained. Mw of thepolymer obtained was 599×10⁴, Mn was 294×10⁴, Mw/Mn was 2.0, no crystalfusion peak by DSC was detected, and the polymer was amorphous. Theglass transition temperature was observed at −61° C.

Comparative Example 1

[0105] An egg-plant type flask with an inner volume of 50 ml wasreplaced with argon, and 1 mmol of MMAO was added therein.

[0106] On the other hand, in an egg-plant type flask with an innervolume of 25 ml replaced with argon, 2 ml of purified toluene and 4.8 mgof dichloro{2,2′-thiobis[4-methyl-6-(tert-butyl)phenolato} titanium weremixed by stirring, and then charged into the above-mentioned egg-planttype flask of 50 ml. The molar ratio of [Al]/[Ti] of the catalystsolution prepared then was 100. After the catalyst solution was mixed bystirring at room temperature for 10 minutes, 6.3 ml of 1-hexene wascharged and the polymerization was carried out at 40° C. for 1 hour.After completion of the polymerization, the contents of the flask werecharged into about 400 ml of an acidic methanol, and the precipitatedpolymer was filtered to be dried at 80° C. for about 2 hours. As aresult, 0.31 g of poly(1-hexene) was obtained. Mw of poly(1-hexene)obtained was 20×10⁴ Mn was 8×10⁴, Mw/Mn was 2.5.

[0107] As described above, according to the present invention, anamorphous polymer having a high molecular weight enough to improveproblems such as stickiness and elution to an organic solvent and toexhibit an elastomeric property, and substantially not having a meltingpoint, and a process for producing the amorphous polymer, are provided.

What is claimed is:
 1. A process for producing an olefin polymer of analkenyl hydrocarbon having 5 or more carbon atoms, wherein said olefinpolymer has a polystyrene-reduced number average molecular weight of300,000 or more, and a molecular weight distribution of 2.40 or less interms of ratio of polystyrene-reduced weight average molecular weight topolystyrene-reduced number average molecular weight, and is an amorphouspolymer substantially not having a melting point, comprising:polymerizing an alkenyl hydrocarbon having 5 or more carbon atoms withan olefin polymerization catalyst obtained by contacting: a transitionmetal compound (A) represented by the formula (1) described below;

wherein, M represents a transition metal atom of the Fourth Group of thePeriodic Table; X and Y independently represent a hydrogen atom, ahalogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxygroup, an aryloxy group, an aralkyloxy group, a sulfonyloxy group, adi-substituted amino group or a substituted silyl group; R¹, R², R³, R⁴,R⁵, R⁶, R⁷ and R⁸ independently represent a hydrogen atom, an alkylgroup, an aryl group, an aralkyl group, an alkoxy group, an aryloxygroup, an aralkyloxy group, a di-substituted amino group or asubstituted silyl group; R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ may be optionallybonded to form a ring; T represents a divalent covalent crosslinkinggroup having 1 to 20 carbon atoms, or a divalent group represented by—O—, —S—, —S—S—, —S(═O)—, —S(═O)₂—, —C(═O)—, —N(R⁹)—, —P(R⁹)— or —P(═O)(R⁹)—, wherein R⁹ represents a hydrogen atom or a hydrocarbon grouphaving 1 to 6 carbon atoms; and n is an integer of from 0 to 3; anorganoaluminumoxy compound (B) soluble in an aromatic solvent; and water(C), wherein the molar ratio of aluminum atom contained in theorganoaluminumoxy compound (B) to a transition metal atom contained inthe transition metal compound (A) is 1 to 20000, and the amount of waterused is 0.1 to 3.0 mol per aluminum atom contained in theorganoaluminumoxy compound (B).
 2. The process according to claim 1 ,wherein T is a divalent group represented by —S—.
 3. The processaccording to claim 1 , wherein the organoaluminumoxy compound (B)soluble in an aromatic solvent is methylisobutylalumoxane.
 4. Theprocess according to claim 1 , wherein the organoaluminumoxy compound(B) soluble in an aromtaic hydrocarbon solvent is an organoaluminumoxycompound represented by formula (4) or (5):

wherein R represents methyl group or isobutyl group, the presence ratioof methyl group and isobutyl group is methyl group: isobutyl group=5 to95:95 to 5; Al represents aluminum atom; and m represents a number of 1to
 5. 5. The process according to claim 1 , wherein the amount oforganoaluminumoxy (B) is 100 to 20,000 mol in terms of aluminum atomcontained in the organoaluminumoxy compound per one mol of thetransition metal atom contained the the transition metal compound (A)and the amount of the water (C) is 0.1 to 1.0 mol per one mol of analuminum atom contained in the organoaluminumoxy compound (B).
 6. Theprocess according to claim 1 , wherein the alkenyl hydrocarbon having 5or more carbon atoms is 1-hexene or 1-octene.